compounds useful for dyeing nylon, wool, and leather, having the formula: ##STR1## wherein X1 is chlorine, bromine, methyl or trifluoromethyl, Y3 is chlorine or bromine, and K1 is a radical of the formula ##STR2## where R3 is C2 to C4 hydroxyalkyl, methoxyethyl or methoxypropyl.
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The present invention relates to compounds which, in the form of the free acids, are of the general formula I ##STR3## where X is fluorine, chlorine, bromine, methyl, trifluoromethyl, C1 -C4 -alkylsulfonyl, arylsulfonyl, acetyl or benzoyl, Y is hydrogen, fluorine, chlorine, bromine, sulfamyl, C1 -C4 -mono- or -dialkylsulfamyl, C1 -C4 -alkylsulfonyl, methyl or trifluoromethyl, Y1 is hydrogen, hydroxysulfonyl, methyl or chlorine, Y2 is hydrogen or hydroxysulfonyl and K is a radical of the formula ##STR4## either Y1 or Y2 being hydroxysulfonyl, and T is cyano or methylsulfonyl, R is hydrogen or C1 -C3 -alkyl, R1 is hydrogen or alkyl or is benzyl, sulfobenzyl, phenylethyl, sulfophenylethyl, sulfophenylpropyl or C1 -C10 -alkyl which is unsubstituted or substituted by hydroxyl, cyano, C1 -C4 -alkanoyloxy or C1 -C8 -alkoxy, or is a radical of the formula ##STR5## R2 is hydrogen or C1 -C8 -alkyl, R3 is hydrogen or allyl, or is C1 -C10 -alkyl which may or may not be interrupted by oxygen and is unsubstituted or substituted by hydroxyl, cyano, C1 -C4 -alkanoyloxy, C1 -C8 -alkoxy, cyclohexyloxy, phenyl, phenoxy, sulfophenoxy, sulfophenyl or hydroxysulfonyloxy, or is cyclopentyl, or is cyclohexyl which is unsubstituted or substituted by hydroxyl, hydroxyethoxy or methyl, or is pyrrolidonylalkyl, phenyl, methoxyphenyl, sulfophenyl, C1 -C4 -alkoxysulfophenyl or a radical of the formula ##STR6## or R2 and R3, together with the nitrogen, form a saturated 5-membered or 6-membered ring, Z is phenyl which is unsubstituted or substituted by chlorine, methyl, methoxy or acetylamino, and A is a C2 -C10 -alkyl radical which may or may not be interrupted by oxygen.
Radicals R are, in addition to hydrogen, ethyl, propyl or, preferably, methyl. In addition to those already mentioned, specific examples of radicals R1, R2 and R3 (where these fall under the general definition) are:
1. Unsubstituted or substituted alkyl radicals: ##STR7##
2. unsubstituted or substituted cycloalkyl radicals ##STR8##
3. Aralkyl radicals: ##STR9## and those containing C6 H4 CH3 instead of C6 H5.
4. Sulfophenyl radicals: ##STR10##
5. ##STR11## where n is 2, 3, 4 or 6, C2 H4 OCHO, C2 H4 OCOC2 H5, C2 H4 OCOCH3, (C2 H4 O)2 COCH3, (C2 H4 O)2 CHO, (CH2)3 OCOCH3, C3 H6 OCOC2 H5 and (CH2)3 OCHO.
Examples of preferred substituents R1 and R3 are: ##STR12##
Within the scope of the general definitions, specific examples of radicals X and Y, in addition to those stated above, are methyl, ethyl, butyl, phenyl, tolylsulfonyl and the radicals of the formulae SO2 NHCH3, SO2 NHC2 H5, SO2 NHC3 H7, SO2 NHC4 H9, SO2 N(CH3)2, SO2 N(C2 H5)2, SO2 N(C3 H7)2 or SO2 N(C4 H9)2.
The dyes according to the invention can be prepared by diazotizing a diazo component of an amine of the formula ##STR13## by a conventional method, and reacting the resulting diazonium salt with a coupling component of the formula H--K.
Of particular importance are compounds of formula Ia ##STR14## where X1 is chlorine, bromine, methyl or trifluoromethyl, and K1 is a radical of the formula ##STR15## where R3 has the stated meanings.
Other useful compounds are those of the formula Ib ##STR16## where K1, X1 and Y3 have the meanings given in the case of formula Ia.
Dyes of the formula Ia which possess only one sulfo group are particularly suitable for producing level dyeings on nylon. Because of their fast rate of dyeing, they are particularly suitable for trichromatic dyeing.
The good lightfastness on wool, the advantageous phototropic behavior and the very good levelness are also noteworthy.
Some compounds according to the invention are also useful for dyeing leather.
In the Examples which follow, parts and percentages are by weight, unless stated otherwise.
PAC (A) 2,4-Dichloroacetanilide396 parts by volume of sulfuryl chloride are added to 270 parts of acetanilide in 1000 parts by volume of nitrobenzene in the course of 3 hours at from 50° to 70°C (the chlorination is begun at a low temperature, which is then increased in order to suppress the precipitation of 2,4-dichloroacetanilide). When the addition of sulfuryl chloride is complete, stirring is continued for 1 hour from 70° to 75°C, after which dissolved hydrogen chloride is blown out with nitrogen. The mixture is then left to cool, whereupon 2,4-dichloroacetanilide is precipitated, and is isolated by being filtered off.
The product can be washed with water and dried to give 330 parts of 2,4-dichloroacetanilide, which contains about 5% of 2,4,6-trichloroacetanilide. If the nitrobenzene which is recovered as a filtrate, and in which some 2,4-dichloroacetanilide is still dissolved, is employed in a second experiment, the yield increases to 396 parts.
204 parts of the crude 2,4-dichloroacetanilide are added to 300 parts of 100% strength sulfuric acid, while stirring. Thereafter, the mixture is heated further to 130°C, and 235 parts of chlorosulfonic acid are added dropwise at this temperature in such a manner that the hydrogen chloride gas liberated can readily be removed. Stirring is then continued at from 135° to 140°C until the sulfonation is complete, this taking about 1 hour. The mixture is then left to cool to 50°-80°C, and is poured into 1300 parts by volume of water. After steam distillation for a short time, 10 parts of pure 2,4,6-trichloroaniline are obtained, as a by-product, in the distillate. The reaction mixture is then cooled to room temperature, and precipitated 2,4-dichloroaniline-6-sulfonic acid is filtered off and washed with dilute hydrochloric acid. 204 parts of 2,4-dichloroaniline-6-sulfonic acid (calculated as 100% pure) are obtained as a colorless aqueous paste, which can be used in moist form for diazotizations. H-NMR in D2 O: 7.3 ppm, 7.6 ppm, J: 3 Hz (as the ammonium salt).
204 parts of crude 2,4-dichloroacetanilide are carefully added to 600 parts of 23% strength oleum, and the mixture is heated to 140°C and stirred at this temperature for 1 hour. It is then left to cool to 50°-80°C and is poured into 1000 parts of water. 10 parts of 2,4,6-trichloroaniline are isolated by steam distillation, and the remaining mixture is filtered after it has cooled. The gray product isolated is stirred with about 5000 parts of water and neutralized with sodium hydroxide solution. A little active carbon is added, after which the mixture is heated to about 95°C and filtered, and the resulting 2,4-dichloroaniline-5-sulfonic acid is precipitated from the filtrate by acidification and is isolated in a conventional manner after the mixture has cooled. The product still contains a small amount of 2,4-dichloroaniline-6-sulfonic acid, which can be removed by recrystallization from water. 2,4-Dichloroaniline-5-sulfonic acid is obtained as a colorless powder. Yield: about 140 parts. H-NMR in D2 O: 7.45 ppm (as the ammonium salt).
19.5 parts of 2,4-dichloroaniline-6-sulfonic acid are dissolved in 200 parts by volume of hot water at pH 7.5-10, using sodium hydroxide solution. A wetting agent which is effective under acidic conditions and 27 parts by volume of a 23% strength aqueous sodium nitrite solution are added, and the mixture is cooled to 0°-5°C 60 parts of ice are added, after which 55 parts of a 15-18% strength hydrochloric acid solution are introduced all at once, and the mixture is stirred for a further 3 hours at from 0° to 5°C Thereafter, a solution or suspension of 21.2 parts of 2,6-bis-(3-hydroxypropylamino)-3-cyano-4-methylpyridine in 120 parts by volume of water and 7 parts by volume of concentrated hydrochloric acid is run in, stirring is continued for from 15 to 30 minutes, and the pH of the mixture is then slowly increased to 2-2.5 by adding sodium hydroxide solution or sodium formate. The acid formed as a result of the coupling reaction is then bound continuously by adding appropriate amounts of sodium hydroxide solution or sodium formate. When the reaction has been maintained at pH 2-2.5 for about 30-60 minutes, the pH of the mixture is increased to 3-3.5 by adding dilute sodium hydroxide solution or sodium acetate, and stirring is continued at this pH until the coupling is substantially complete. The pH of the mixture is then increased to 4.3-4.7 by adding dilute sodium hydroxide solution, after which the coupling reaction quickly ends. The resulting dye of the formula ##STR17## is precipitated virtually quantitatively by adding 80 parts of sodium chloride, and is then isolated by filtration. It is dried to give 42 parts of a reddish brown powder which still contains about 1 part of water-soluble salts in addition to 41 parts of the dye.
The dye dissolves in water to give a yellow solution and dyes nylon and wool in intense, lightfast, golden yellow hues. The absorption maximum of a solution of about 0.020 part of dye in 900 parts by volume of dimethylformamide and 150 parts by volume of glacial acetic acid is 427.5 nm.
The particular advantage of this dye is the high migrating power and the ability to dye nylon simultaneously with red and blue dyes. For example, a dye mixture of about 4 parts of this dye with about 4 parts of Acid Red 57 and 3 parts of Acid Blue 72 gives a (dark) brown. All three dyes dye nylon fabric at the same rate in the temperature range from 60° to 100°C, so that the dyeing always remains brown. The dye is also suitable for combination dyeing to achieve beige hues which are very light-fast and in particular are non-phototropic to light from incandescent lamps (no reversible change to a greener hue).
19.5 parts of 2,4-dichloroaniline-6-sulfonic acid are diazotized by a procedure similar to that described in Example 1. Excess nitrous acid is then destroyed in a conventional manner, and the diazonium salt mixture is buffered to pH 2-4 with sodium acetate. A solution of 16.7 parts of 1-(2-methoxyethyl)-6-hydroxy-3-cyano-4-methylpyrid-2-one in 200 parts by volume of water, 10 parts of 50% strength sodium hydroxide solution and 0.3 part of a dispersant which is effective under acidic conditions is then run in. The coupling mixture is stirred for a further 60-80 minutes, after which it is acidified to pH 0.3-0.5 with concentrated hydrochloric acid, and the precipitated dye of the formula ##STR18## is filtered off under suction, washed salt-free with a little water and dried to give 36 parts of a yellow powder. 20 parts of this powder are suspended in a mixture of 20 parts of butyldiglycol and 60 parts of 2- or 3-methoxypropanol, and the suspension is neutralized with lithium hydroxide. Clear filtration gives a honey yellow solution. This dye solution is very useful for dyeing leather lemon yellow by a conventional spray-dyeing method. The absorption maximum of the dye in a 9:1 dimethylformamide/glacial acetic acid mixture is determined as 412 nm.
22.1 parts of 2-trifluoromethyl-4-chloroaniline-6-sulfonic acid are diazotized by a procedure similar to that described in Example 1. 31 parts of the coupling component of the formula ##STR19## in the form of a roughly 50% strength water-moist paste, are then introduced into the diazonium salt mixture, after which the pH of the coupling mixture is brought to 4.5-5 with 25% strength sodium hydroxide solution. When coupling is complete, the mixture is neutralized with further sodium hydroxide solution and is then spray dried.
73 parts of a red powder are obtained. The resulting dye is of the formula ##STR20## and has an absorption maximum of 430 nm in a 9:1 dimethylformamide/glacial acetic acid mixture. It dyes wool and nylon in fast intense golden yellow hues.
19.5 parts of 2,4-dichloroaniline-6-sulfonic acid are diazotized by a procedure similar to that described in Example 1. When excess nitrous acid has been destroyed, 24.2 parts of 2-phenyl-4,6-bis-(3-hydroxypropylamino)-pyrimidine are added, and stirring is continued until the coupling component has dissolved. Thereafter, a dispersant which is highly effective at pH 7-10 is added and the pH of the coupling mixture is brought to 8.5-9.2 with sodium hydroxide solution and then with a little sodium carbonate solution (as a buffer). Stirring is continued overnight, and the resulting dye of the formula ##STR21## (λmax: 431.5 nm (CH3)2 NCHO/CH3 CO2 H=9:1) is then precipitated by adding about 30 parts of sodium chloride and acidifying the mixture to pH 4-4.5, and is isolated in a conventional manner to give about 50 parts of a reddish brown powder which dissolves in water to give a yellow solution and dyes nylon fabric and wool in very fast golden yellow hues. The dye has great migrating power.
| TABLE 1 |
| __________________________________________________________________________ |
| ##STR22## |
| λmax |
| No. |
| R R1 R2 R3 |
| Hue (nm) |
| __________________________________________________________________________ |
| 1 Cl H C3 H6 OCH3 |
| C3 H7 |
| yellow 413 |
| 2 Cl H C3 H6 OH |
| C3 H7 |
| yellow 413 |
| 3 Cl H C3 H6 OC4 H8 OH |
| CH3 |
| yellow 411 |
| 4 Cl H C3 H6 OC4 H8 OH |
| H yellow 412 |
| 5 Cl H C2 H4 OC2 H4 OH |
| CH3 |
| yellow 409 |
| 6 Cl H C2 H4 OC2 H4 OCH3 |
| CH3 |
| yellow 409 |
| 7 Cl H C2 H4 OC4 H9 (n) |
| CH3 |
| yellow 409 |
| 8 Cl H C3 H6 OCH3 |
| CH3 |
| yellow 410 |
| 9 Cl H C3 H6 OC2 H5 |
| CH3 |
| yellow 410 |
| 10 Cl C3 H6 OC4 H8 OH |
| H CH3 |
| yellow 412 |
| 11 Cl C3 H6 OC2 H4 OC2 H5 |
| H CH3 |
| yellow 411 |
| 12 Cl C2 H5 |
| C2 H4 OH |
| CH3 |
| golden yellow |
| 422 |
| 13 Cl CH3 C3 H6 OC4 H8 OH |
| CH3 |
| golden yellow |
| 420 |
| 14 Cl C2 H5 |
| C3 H6 OC4 H8 OH |
| CH3 |
| golden yellow |
| 422 |
| 15 Cl C2 H5 |
| C2 H4 OC2 H4 OH |
| CH3 |
| golden yellow |
| 421 |
| 16 Cl CH2 CHCH2 |
| C2 H4 OC2 H4 OH |
| CH3 |
| golden yellow |
| 422 |
| 17 Cl CH(CH3)2 |
| C2 H4 OC2 H4 OH |
| CH3 |
| golden yellow |
| 420 |
| 18 Cl CH2 CH2 OCH3 |
| CH2 CH2 OCH3 |
| CH 3 |
| golden yellow |
| 419 |
| 19 Cl (CH2)3 OCH3 |
| CH2 CH2 OCH3 |
| CH3 |
| golden yellow |
| 421 |
| 20 Cl (CH2)3 OCH3 |
| (CH2)3 OCH3 |
| CH3 |
| golden yellow |
| 427 |
| 21 Cl |
| ##STR23## |
| C2 H4 OCH3 |
| CH3 |
| golden yellow |
| 422 |
| 22 Cl CH2 CH2 OCH3 |
| (CH2)3 OCH3 |
| CH3 |
| golden yellow |
| 423 |
| 23 Cl CH2 CH2 OCH3 |
| CH2 CH2 OH |
| CH3 |
| golden yellow |
| 423 |
| 24 Cl CH2 CH2 OCH3 |
| ##STR24## CH3 |
| golden yellow |
| 423 |
| 25 Cl CH2 CH2 OCH3 |
| CH2 CH2 OC2 H5 |
| CH3 |
| golden yellow |
| 421 |
| 26 Cl CH2 CH2 OCH3 |
| (CH2)3 OCH(CH3)2 |
| CH3 |
| golden yellow |
| 423 |
| 27 Cl CH2 CH2 OCH3 |
| (CH2)3 O(CH2)4 OH |
| CH3 |
| golden yellow |
| 423 |
| 28 Cl CH2 CH2 OCH 3 |
| (CH2)3 OH |
| CH3 |
| golden yellow |
| 424 |
| 29 Cl |
| ##STR25## |
| CH2 CH2 OCH3 |
| CH3 |
| golden yellow |
| 423 |
| 30 Cl |
| ##STR26## |
| (CH2)3 OCH3 |
| CH3 |
| orange 423 |
| 31 Cl |
| ##STR27## |
| (CH2)2 OH |
| CH3 |
| golden yellow |
| 422 |
| 32 Cl |
| ##STR28## |
| (CH2)3 OH |
| CH3 |
| orange 424 |
| 33 Cl |
| ##STR29## |
| (CH2)3 OC2 H5 |
| CH3 |
| orange 424 |
| 34 Cl |
| ##STR30## |
| ##STR31## CH3 |
| orange 424 |
| 35 Cl (CH2)3 OH |
| (CH2)2 OH |
| CH3 |
| golden yellow |
| 425 |
| 36 Cl (CH2)3 OH |
| ##STR32## CH3 |
| golden yellow |
| 426 |
| 37 Cl (CH2)3 OH |
| (CH2)2 OCH3 |
| CH3 |
| golden yellow |
| 426 |
| 38 Cl (CH2)3 OH |
| (CH2)3 OCH3 |
| CH3 |
| golden yellow |
| 427 |
| 39 Cl (CH2)3 OH |
| (CH2)3 OC2 H5 |
| CH3 |
| golden yellow |
| 426 |
| 40 Cl (CH2)2 OH |
| (CH2)2 OH |
| CH3 |
| golden yellow |
| 420 |
| 41 Cl (CH2)2 OH |
| (CH2)3 OH |
| CH3 |
| golden yellow |
| 423 |
| 42 Cl (CH2)2 OH |
| ##STR33## CH3 |
| golden yellow |
| 423 |
| 43 Cl (CH2)2 OH |
| (CH2)2 OCH3 |
| CH3 |
| golden yellow |
| 421 |
| 44 Cl (CH2)2 OH |
| (CH2)3 OCH3 |
| CH3 |
| golden yellow |
| 423 |
| 45 Cl (CH2)2 OH |
| (CH2)3 OC2 H5 |
| CH3 |
| golden yellow |
| 423 |
| 46 Cl (CH2)2 OH |
| C4 H9 (n) |
| CH3 |
| golden yellow |
| 427 |
| 47 Cl (CH2)2 OH |
| (CH2)3 OCH2 C6 H5 |
| CH3 |
| golden yellow |
| 425 |
| 48 Cl (CH2)2 OH |
| (CH2)2 C6 H5 |
| CH3 |
| golden yellow |
| 422 |
| 49 Cl (CH2)2 OH |
| ##STR34## CH3 |
| golden yellow |
| 422 |
| 50 Cl (CH2)2 OH |
| ##STR35## CH3 |
| golden yellow |
| 423 |
| 51 Cl C2 H5 |
| ##STR36## CH3 |
| golden yellow |
| 422 |
| 52 Cl C2 H5 |
| C2 H5 |
| CH3 |
| golden yellow |
| 420 |
| 53 Cl (CH2)2 CN |
| (CH2)3 OH |
| CH3 |
| golden yellow |
| 422 |
| 54 Cl (CH2)5 CN |
| (CH2)3 OH |
| CH3 |
| golden yellow |
| 423 |
| 55 Cl (CH2)2 C6 H5 |
| (CH2)2 OH |
| CH3 |
| golden yellow |
| 421 |
| 56 Cl |
| ##STR37## |
| C4 H9 (n) |
| CH3 |
| golden yellow |
| 423 |
| 57 Cl CH2 CHCH2 |
| (CH2)2 OH |
| CH3 |
| golden yellow |
| 422 |
| 58 Cl CH2 CHCH2 |
| (CH2)3 OH |
| CH3 |
| golden yellow |
| 423 |
| 59 Br (CH2)3 OH |
| (CH2)3 OH |
| CH3 |
| golden yellow |
| 429 |
| 60 CF3 |
| (CH2)3 OH |
| (CH2)3 OH |
| CH3 |
| golden yellow |
| 430 |
| 61 CF3 |
| (CH2)2 OCH3 |
| (CH2)2 OH |
| CH3 |
| golden yellow |
| 428 |
| 62 Cl |
| ##STR38## |
| (CH2)2 OH |
| CH3 |
| golden yellow |
| 425 |
| 63 Cl |
| ##STR39## |
| (CH2)3 OH |
| CH3 |
| golden yellow |
| 426 |
| 64 Cl |
| ##STR40## |
| (CH2)3 OH |
| CH3 |
| golden yellow |
| 426 |
| 65 Cl |
| ##STR41## |
| (CH2)2 OH |
| CH3 |
| golden yellow |
| 424 |
| 66 Cl (CH2 )2 OCOCH3 |
| (CH2)2 OCOCH3 |
| CH3 |
| golden yellow |
| 420 |
| 67 Cl (CH2)3 OCHO |
| (CH2)3 OCHO |
| CH3 |
| golden yellow |
| 421 |
| 68 Cl (CH2)2 OCH3 |
| (CH2)3 OCHO |
| CH3 |
| golden yellow |
| 421 |
| 69 Cl (CH2)3 OCHO |
| (CH2)2 OCH3 |
| CH3 |
| golden yellow |
| 421 |
| 70 Cl (CH2)4 OH |
| (CH2)4 OH |
| CH3 |
| golden yellow |
| 430 |
| 71 Cl (CH2)4 OH |
| (CH2)3 OH |
| CH3 |
| golden yellow |
| 429 |
| 72 Cl (CH2)4 OH |
| (CH2)2 OH |
| CH3 |
| golden yellow |
| 429 |
| 73 Cl (CH2)4 OH |
| (CH2)2 OCH3 |
| CH3 |
| golden yellow |
| 428 |
| __________________________________________________________________________ |
| TABLE 2 |
| __________________________________________________________________________ |
| ##STR42## |
| No. |
| R1 R2 R3 |
| Hue |
| __________________________________________________________________________ |
| ##STR43## C2 H5 |
| H golden yellow |
| 2 |
| ##STR44## C2 H5 |
| C2 H5 |
| orange |
| 3 |
| ##STR45## C4 H9 (n) |
| H golden yellow |
| 4 |
| ##STR46## C3 H6 OCH3 |
| H golden yellow |
| 5 |
| ##STR47## C2 H4 OCH3 |
| H golden yellow |
| 6 |
| ##STR48## C3 H6 OC2 H5 |
| H golden yellow |
| 7 |
| ##STR49## C3 H6 OH |
| H golden yellow |
| 8 |
| ##STR50## C4 H8 OH |
| H golden yellow |
| 9 |
| ##STR51## C4 H9 (n) |
| C4 H9 (n) |
| orange |
| 10 |
| ##STR52## |
| ##STR53## |
| H golden yellow |
| 11 |
| ##STR54## C2 H4 OH |
| H golden yellow |
| 12 |
| ##STR55## C3 H6 OH |
| H golden yellow |
| 13 |
| ##STR56## C4 H9 (n) |
| H golden yellow |
| 14 |
| ##STR57## C3 H6 OCH3 |
| H golden yellow |
| 15 |
| ##STR58## C2 H4 OCH3 |
| H golden yellow |
| 16 |
| ##STR59## |
| ##STR60## |
| H golden yellow |
| 17 C4 H8 OH |
| ##STR61## |
| H golden yellow |
| 18 C3 H6 OH |
| ##STR62## orange |
| 19 C2 H4 OCH3 |
| ##STR63## orange |
| 20 C3 H6 OCH3 |
| ##STR64## orange |
| 21 C3 H6 OH |
| ##STR65## orange |
| __________________________________________________________________________ |
| TABLE 3 |
| __________________________________________________________________________ |
| ##STR66## |
| λmax |
| No. |
| R R1 R2 R3 Hue (nm) |
| __________________________________________________________________________ |
| 1 Cl C3 H6 OH |
| C6 H5 |
| C2 H4 OH |
| golden yellow |
| 429 |
| 2 Cl C3 H6 OH |
| C6 H5 |
| C2 H4 OCH3 |
| golden yellow |
| 428 |
| 3 Cl C3 H6 OH |
| C6 H5 |
| C3 H6 OCH3 |
| golden yellow |
| 430 |
| 4 Cl C3 H6 OH |
| C6 H5 |
| C2 H4 OC2 H5 |
| golden yellow |
| 428 |
| 5 Cl C3 H6 OH |
| C6 H5 |
| C2 H4 OC2 H4 OH |
| yellow 427 |
| 6 Cl C3 H6 OH |
| C6 H5 |
| C2 H4 OC2 H4 OCH3 |
| yellow 427 |
| 7 Cl C3 H6 OH |
| C6 H5 |
| C3 H6 OC2 H4 OH |
| golden yellow |
| 430 |
| 8 Cl C3 H6 OH |
| C6 H5 |
| C3 H6 OC4 H8 OH |
| golden yellow |
| 430 |
| 9 Cl C2 H4 OH |
| C6 H5 |
| C2 H4 OCH3 |
| yellow 426 |
| 10 Cl C2 H4 OH |
| C6 H5 |
| C3 H6 OCH3 |
| yellow 427 |
| 11 Cl C2 H4 OH |
| C6 H5 |
| C3 H6 OC3 H7 |
| yellow 428 |
| 12 Cl C2 H4 OCH3 |
| C6 H5 |
| C2 H4 OCH3 |
| yellow 426 |
| 13 Cl C2 H4 OCH3 |
| C6 H5 |
| C3 H6 OCH3 |
| yellow 428 |
| 14 Cl C3 H6 OCH3 |
| C6 H5 |
| C3 H6 OCH3 |
| golden yellow |
| 429 |
| 15 Cl |
| ##STR67## C6 H5 |
| C3 H6 OCH3 |
| golden yellow |
| 430 |
| 16 Cl |
| ##STR68## C6 H5 |
| ##STR69## |
| golden yellow |
| 431 |
| 17 Br |
| ##STR70## C6 H5 |
| ##STR71## |
| golden yellow |
| 431 |
| 18 Br C3 H6 OH |
| C3 H6 |
| C3 H6 OH |
| golden yellow |
| 432 |
| 19 Cl C3 H6 OH |
| ##STR72## |
| C3 H6 OH |
| golden yellow |
| 432 |
| 20 Cl C3 H6 OH |
| ##STR73## |
| C3 H6 OH |
| golden yellow |
| 432 |
| 21 Cl C4 H8 OH |
| C6 H5 |
| C4 H8 OH |
| golden yellow |
| 433 |
| 22 Cl C2 H4 OH |
| ##STR74## |
| C2 H4 OH |
| golden yellow |
| 431 |
| 23 Cl |
| ##STR75## |
| ##STR76## |
| C2 H4 OH |
| yellow 428 |
| 24 CF3 |
| C3 H6 OH |
| C6 H6 |
| C3 H6 OH |
| golden yellow |
| 434 |
| 25 CF3 |
| C3 H6 OH |
| C6 H5 |
| C2 H4 OH |
| golden yellow |
| 433 |
| 26 CF3 |
| ##STR77## C6 H5 |
| C2 H4 OH |
| golden yellow |
| 433 |
| 27 CF3 |
| ##STR78## C6 H5 |
| ##STR79## |
| golden yellow |
| 435 |
| 28 CF3 |
| C2 H4 OCH3 |
| C6 H5 |
| ##STR80## |
| golden yellow |
| 432 |
| 29 CF3 |
| C2 H4 OCH3 |
| C6 H5 |
| C2 H4 OH |
| golden yellow |
| 432 |
| 30 CF3 |
| C2 H4 OCH3 |
| C6 H5 |
| C3 H6 OH |
| golden yellow |
| 432 |
| 31 CF3 |
| C 3 H6 OCH3 |
| C6 H5 |
| C3 H6 OH |
| golden yellow |
| 435 |
| 32 CF3 |
| ##STR81## |
| ##STR82## |
| C2 H4 OH |
| golden yellow |
| 433 |
| 33 Cl |
| ##STR83## C6 H5 |
| ##STR84## |
| golden yellow |
| 434 |
| 34 CH3 |
| C2 H4 OH |
| C6 H5 |
| C2 H4 OH |
| golden yellow |
| 432 |
| __________________________________________________________________________ |
| TABLE 4 |
| ______________________________________ |
| ##STR85## |
| λmax |
| No. R R1 R2 R3 |
| Hue (nm) |
| ______________________________________ |
| 1Cl Cl C2 H4 OH |
| H green- |
| 412 |
| ish |
| yellow |
| 2Cl Cl C2 H4 OH |
| CH3 |
| green- |
| 412 |
| ish |
| yellow |
| 3Cl Cl C2 H4 OH |
| C2 H5 |
| green- |
| 411 |
| ish |
| yellow |
| 4Cl Cl C2 H4 OH |
| C3 H7 |
| green- |
| 410 |
| (n) ish |
| yellow |
| 5Cl Cl C3 H6 OH |
| CH3 |
| green- |
| 412 |
| ish |
| yellow |
| 6Cl Cl C3 H6 OH |
| CH3 |
| green- |
| 412 |
| ish |
| yellow |
| 7Cl Cl C3 H6 OH |
| C3 H7 |
| green- |
| 411 |
| (n) ish |
| yellow |
| 8Cl Cl C3 H6 OCOCH3 |
| CH3 |
| green- |
| 413 |
| ish |
| yellow |
| 9Cl Cl C3 H6 OCH3 |
| C3 H7 |
| green- |
| 412 |
| (n) ish |
| yellow |
| 10Cl Cl C3 H6 OCH3 |
| CH3 |
| green- |
| 412 |
| ish |
| yellow |
| 11Br Cl C3 H6 OCH3 |
| CH3 |
| green- |
| 413 |
| ish |
| yellow |
| 12Cl Cl C3 H6 OCH3 |
| H green- |
| 412 |
| ish |
| yellow |
| 13Cl Cl C6 H13 (n) |
| CH3 |
| green- |
| 413 |
| ish |
| yellow |
| 14Cl Cl C3 H6 OC2 H5 |
| CH3 |
| green- |
| 413 |
| ish |
| yellow |
| 15Cl Cl C3 H6 OC3 H7 |
| CH3 |
| green- |
| 412 |
| ish |
| yellow |
| 16Cl Cl C3 H6 OC4 H8 OH |
| CH3 |
| green- |
| 412 |
| ish |
| yellow |
| 17Cl CF3 C3 H6 OC4 H8 OH |
| CH3 |
| green- |
| 407 |
| ish |
| yellow |
| 18Cl CF3 C6 H12 OH |
| CH3 |
| green- |
| 408 |
| ish |
| yellow |
| 19Cl Cl C6 H12 OH |
| CH3 |
| green- |
| 413 |
| ish |
| yellow |
| 20Cl CF3 C3 H6 OCH3 |
| CH3 |
| green- |
| 407 |
| ish |
| yellow |
| 21Cl CF3 CH2 CH2C6 H5 |
| CH3 |
| green- |
| 407 |
| ish |
| yellow |
| 22Cl CF3 CH2 CHCH2 |
| CH3 |
| green- |
| 407 |
| ish |
| yellow |
| 23Cl CF3 C6 H13 (n) |
| CH3 |
| green- |
| 408 |
| ish |
| yellow |
| 24Cl CF3 |
| ##STR86## CH3 |
| green- ish yellow |
| 407 |
| 25Cl Cl |
| ##STR87## CH3 |
| green- ish yellow |
| 412 |
| 26Cl Cl |
| ##STR88## CH3 |
| green- ish yellow |
| 413 |
| 27Cl Cl C4 H8 OH |
| CH3 |
| green- |
| 413 |
| ish |
| yellow |
| 28Cl Cl C6 H12 OH |
| CH3 |
| green- |
| 413 |
| ish |
| yellow |
| 29H SO2 C6 H5 |
| C4 H8 OH |
| CH3 |
| green- |
| ish |
| yellow |
| 30H SO2 C6 H5 |
| C3 H6 OH |
| CH3 |
| green- |
| ish |
| yellow |
| 31Cl CH3 C3 H6 OH |
| CH3 |
| green- |
| 411 |
| ish |
| yellow |
| 32Cl CH3 C2 H4 OH |
| CH3 |
| green- |
| 412 |
| ish |
| yellow |
| 33Cl CH3 C3 H6 OCH3 |
| CH3 |
| green- |
| 411 |
| ish |
| yellow |
| 34Cl Br C3 H6 OCH3 |
| CH3 |
| green- |
| 413 |
| ish |
| yellow |
| 35Cl Br C3 H6 OH |
| CH3 |
| green- |
| 413 |
| ish |
| yellow |
| 36Cl Br C4 H8 OH |
| CH3 |
| green- |
| 413 |
| ish |
| yellow |
| 37CH3 |
| Br C4 H8 OH |
| CH3 |
| green- |
| 414 |
| ish |
| yellow |
| 38CH3 |
| Br C3 H6 OH |
| CH3 |
| green- |
| 414 |
| ish |
| yellow |
| 39CH3 |
| Br C3 H6 OCH 3 |
| CH3 |
| green- |
| 414 |
| ish |
| yellow |
| 40CH3 |
| Br C2 H4 OCH3 |
| CH3 |
| green- |
| 414 |
| ish |
| yellow |
| ______________________________________ |
| TABLE 5 |
| ______________________________________ |
| ##STR89## |
| λmax |
| No. R A Hue (nm) |
| ______________________________________ |
| 1 Cl C2 H4 greenish |
| 413 |
| yellow |
| 2 Cl C3 H6 greenish |
| 413 |
| yellow |
| 3 Cl |
| ##STR90## greenish yellow |
| 413 |
| 4 Cl (CH2)6 greenish |
| 412 |
| yellow |
| 5 Cl (CH2)3 O(CH2)3 |
| greenish |
| 413 |
| yellow |
| 6 Br (CH2)3 O(CH2)2 O(CH2)3 |
| greenish |
| 413 |
| yellow |
| 7 Br C3 H6 greenish |
| 413 |
| yellow |
| 8 CF3 |
| C2 H4 greenish |
| 417 |
| yellow |
| 9 CF3 |
| C3 H6 greenish |
| 408 |
| yellow |
| 10 CF3 |
| ##STR91## greenish yellow |
| 408 |
| 11 CF3 |
| (CH2)6 greenish |
| 408 |
| yellow |
| 12 CF3 |
| (CH2)3 O(CH2)3 |
| greenish |
| 408 |
| yellow |
| 13 Cl (CH2)3 O(CH2)2 O(CH2)3 |
| greenish |
| 412 |
| yellow |
| 14 Cl (CH2)3 O(CH2)4 O(CH2)3 |
| greenish |
| 413 |
| yellow |
| 15 Cl CH2(CH3)2CH2 |
| greenish |
| 413 |
| yellow |
| ______________________________________ |
| TABLE 6 |
| ______________________________________ |
| ##STR92## |
| No. A R1 |
| R2 Hue |
| ______________________________________ |
| 1 CH2 CH2 |
| Cl C2 H4 OH |
| golden |
| yellow |
| 2 (CH2)3 Cl C2 H4 OH |
| golden |
| yellow |
| 3 (CH2)3 Cl C3 H6 OH |
| golden |
| yellow |
| 4 (CH2)3 Cl C2 H4 OC2 H4 OH |
| golden |
| yellow |
| 5 (CH2)3 Cl C2 H4 OCH3 |
| golden |
| yellow |
| 6 (CH2)3 Cl C3 H6 OCH3 |
| golden |
| yellow |
| 7 (CH2)4 Cl C2 H4 OH |
| golden |
| yellow |
| 8 (CH2)4 Cl C3 H6 OH |
| golden |
| yellow |
| 9 (CH2)3 O(CH2)2 O(CH2)3 |
| Cl C2 H4 OH |
| golden |
| yellow |
| 10 (CH2)3 O(CH2)2 O(CH2)3 |
| Cl C3 H6 OH |
| golden |
| yellow |
| 11 (CH2)3 O(CH2)4 O(CH2)3 |
| Cl C3 H6 OH |
| golden |
| yellow |
| 12 (CH2)3 O(CH2)4 O(CH2)3 |
| Cl C2 H4 OCH3 |
| golden |
| yellow |
| 13 (CH2) 3 O(CH2)4 O(CH2)3 |
| Cl C3 H6 OCH3 |
| golden |
| yellow |
| 14 (CH2)3 O(CH2)4 O(CH2)3 |
| CF3 |
| C3 H6 OCH3 |
| golden |
| yellow |
| 15 (CH2)3 CF3 |
| C3 H6 OCH3 |
| golden |
| yellow |
| 16 (CH2)6 Cl C2 H4 OCH3 |
| golden |
| yellow |
| 17 |
| ##STR93## Cl C2 H4 OH |
| golden yellow |
| 18 |
| ##STR94## Cl C2 H4 OC2 H4 OH |
| golden yellow |
| 19 (CH2)3 Cl C2 H4 OC2 H4 OH |
| golden |
| yellow |
| 20 (CH2)3 Cl C4 H8 OH |
| golden |
| yellow |
| 21 (CH2)3 CH3 |
| C2 H 4 OH |
| golden |
| yellow |
| ______________________________________ |
| TABLE 7 |
| __________________________________________________________________________ |
| ##STR95## |
| λmax |
| No. |
| R R1 |
| R2 |
| K Hue (nm) |
| __________________________________________________________________________ |
| 1 H CH3 Cl |
| H H Cl |
| SO2 C6 H5 SO2 C6 H5 Cl |
| ##STR96## orange orange orange |
| 4 H CH3 |
| Cl Cl |
| SO2 C6 H5 SO2 C6 H5 |
| ##STR97## orange orange |
| 6 Cl Cl |
| Cl H |
| Cl SO2 C6 H5 |
| ##STR98## orange orange |
| 8 H H H |
| H H H |
| COCH3 CF3 COC6 H5 |
| ##STR99## orange orange orange |
| 11 12 13 |
| H H F |
| H H H |
| COC6 H5 COCH3 Br |
| ##STR100## orange orange orange |
| 14 15 |
| Br Cl |
| H H |
| F F |
| ##STR101## orange orange |
| 16 17 18 19 |
| H Cl SO2 C4 H9 Cl |
| Cl H H Cl |
| Cl SO2 C4 H9 Cl Cl |
| ##STR102## orange orange orange orange |
| 425 |
| 20 21 |
| Cl Cl |
| Cl H |
| Cl CH3 |
| ##STR103## orange orange |
| 425 |
| __________________________________________________________________________ |
| TABLE 8 |
| ______________________________________ |
| ##STR104## |
| λmax |
| No. R1 R2 (nm) |
| ______________________________________ |
| ##STR105## C6 H5 |
| 432 |
| 2 |
| ##STR106## |
| ##STR107## 433 |
| 3 |
| ##STR108## |
| ##STR109## 432 |
| 4 |
| ##STR110## |
| ##STR111## 435 |
| 5 |
| ##STR112## |
| ##STR113## 435 |
| 6 |
| ##STR114## |
| ##STR115## 434 |
| 7 |
| ##STR116## C6 H5 |
| 430 |
| 8 |
| ##STR117## |
| ##STR118## 432 |
| 9 |
| ##STR119## |
| ##STR120## 430 |
| 10 |
| ##STR121## |
| ##STR122## 430 |
| 11 |
| ##STR123## C6 H5 |
| 430 |
| 12 |
| ##STR124## |
| ##STR125## 435 |
| 13 |
| ##STR126## |
| ##STR127## 431 |
| ______________________________________ |
19.5 parts of 2,4-dichloroaniline-5-sulfonic acid are stirred overnight with 50 parts of 15% strength hydrochloric acid in the presence of a wetting agent which is effective under acidic conditions. Thereafter, the mixture is cooled with ice to 0°C, 27 parts by volume of a 23% strength sodium nitrite solution are added in the course of from 5 to 20 minutes, and the suspension is stirred for a further 3 hours at from 0° to 5°C A solution or suspension of 21.2 parts of 2,6-bis-(3-hydroxypropylamino)-3-cyano-4-methylpyridine in 120 parts by volume of water and 7 parts by volume of concentrated hydrochloric acid is then run in. Stirring is continued for from 15 to 30 minutes, and the pH of the mixture is then slowly increased to 1-1.5 by adding sodium hydroxide solution or sodium formate. The acid formed as a result of the coupling reaction is then bound continuously by adding appropriate amounts of sodium hydroxide solution or sodium formate. When the mixture has been kept at pH 1-1.5 for about 30-60 minutes, the pH is increased to 3-3.5 by adding dilute sodium hydroxide solution or sodium acetate. The coupling reaction quickly comes to an end. The resulting dye of the formula ##STR128## is precipitated virtually quantitatively by adding 40 parts of sodium chloride and is then isolated by filtration. After drying, 44 parts of a brown powder are obtained.
The dye dissolves in water to give a yellow solution and dyes nylon and wool in intense, lightfast, golden yellow hues.
The absorption maximum of a solution of about 0.020 part of the dye in 900 parts by volume of dimethylformamide and 150 parts by volume of glacial acetic acid is 457 nm (water: 435 nm).
| TABLE 9 |
| ______________________________________ |
| ##STR129## |
| No. R1 R2 λmax (nm) |
| ______________________________________ |
| ##STR130## C6 H5 |
| 459 |
| 2 |
| ##STR131## |
| ##STR132## 459 |
| 3 |
| ##STR133## |
| ##STR134## 459 |
| 4 |
| ##STR135## |
| ##STR136## 460 |
| 5 |
| ##STR137## |
| ##STR138## 460 |
| 6 |
| ##STR139## |
| ##STR140## 460 |
| 7 |
| ##STR141## C6 H5 |
| 456 |
| 8 |
| ##STR142## |
| ##STR143## 459 |
| 9 |
| ##STR144## |
| ##STR145## 457 |
| 10 |
| ##STR146## |
| ##STR147## 457 |
| 11 |
| ##STR148## C6 H5 |
| 458 |
| 12 |
| ##STR149## |
| ##STR150## 460 |
| 13 |
| ##STR151## |
| ##STR152## 458 |
| ______________________________________ |
| TABLE 10 |
| __________________________________________________________________________ |
| ##STR153## |
| No. |
| R R1 R2 R3 |
| Hue λmax (nm) |
| __________________________________________________________________________ |
| 1 Cl H C3 H6 OCH3 |
| C3 H7 |
| yellow 446 |
| 2 Cl H C3 H6 OH |
| C3 H7 |
| yellow 446 |
| 3 Cl H C3 H6 OC4 H8 OH |
| CH3 |
| yellow 441 |
| 4 Cl H C3 H6 OC4 H8 OH |
| H yellow 443 |
| 5 Cl H C2 H4 OC2 H4 OH |
| CH3 |
| yellow 443 |
| 6 Cl H C2 H4 OC2 H4 OCH3 |
| CH3 |
| yellow 444 |
| 7 Cl H C2 H4 OC4 H9 (n) |
| CH3 |
| yellow 446 |
| 8 |
| Cl H C3 H6 OCH3 |
| CH3 |
| yellow 446 |
| 9 Cl H C3 H6 OC2 H5 |
| CH3 |
| yellow 446 |
| 10 Cl C3 H6 OC4 H8 OH |
| H CH3 |
| yellow 448 |
| 11 Cl C3 H6 OC2 H4 OC2 H5 |
| H CH3 |
| yellow 449 |
| 12 Cl C2 H5 |
| C2 H4 OH |
| CH3 |
| golden yellow |
| 455 |
| 13 Cl CH3 C3 H6 OC4 H8 OH |
| CH3 |
| golden yellow |
| 454 |
| 14 Cl C2 H5 |
| C3 H6 OC4 H8 OH |
| CH3 |
| golden yellow |
| 455 |
| 15 Cl C2 H5 |
| C2 H4 OC2 H4 OH |
| CH3 |
| golden yellow |
| 453 |
| 16 Cl CH2 CHCH2 |
| C2 H4 OC2 H4 OH |
| CH3 |
| golden yellow |
| 454 |
| 17 Cl CH(CH3)2 |
| C2 H4 OC2 H4 OH |
| CH3 |
| golden yellow |
| 453 |
| 18 Cl CH2 CH2 OCH3 |
| CH2 CH2 OCH3 |
| CH3 |
| golden yellow |
| 454 |
| 19 Cl (CH2)3 OCH3 |
| CH2 CH2 OCH3 |
| CH3 |
| golden yellow |
| 455 |
| 20 Cl (CH2)3 OCH3 |
| (CH2)3 OCH3 |
| CH3 |
| golden yellow |
| 456 |
| 21 Cl |
| ##STR154## |
| C2 H4 OCH3 |
| CH3 |
| golden yellow |
| 455 |
| 22 Cl CH2 CH2 OCH3 |
| (CH2)3 OCH3 |
| CH3 |
| golden yellow |
| 455 |
| 23 Cl CH2 CH2 OCH3 |
| CH2 CH2 OH |
| CH3 |
| golden yellow |
| 453 |
| 24 Cl CH2 CH2 OCH3 |
| ##STR155## |
| CH3 |
| golden yellow |
| 453 |
| 25 Cl CH2 CH2 OCH3 |
| CH2 CH2 OC2 H5 |
| CH3 |
| golden yellow |
| 452 |
| 26 Cl CH2 CH2 OCH3 |
| (CH2)3 OCH(CH3)2 |
| CH3 |
| golden yellow |
| 454 |
| 27 Cl CH2 CH2 OCH3 |
| (CH2)3 O(CH2)4 OH |
| CH3 |
| golden yellow |
| 454 |
| 28 Cl CH2 CH2 OCH3 |
| (CH2)3 OH |
| CH3 |
| golden yellow |
| 454 |
| 29 Cl |
| ##STR156## |
| CH2 CH2 OCH3 |
| CH3 |
| golden yellow |
| 452 |
| 30 Cl |
| ##STR157## |
| (CH2)3 OCH3 |
| CH3 |
| orange 453 |
| 31 Cl |
| ##STR158## |
| (CH2)2 OH |
| CH3 |
| golden yellow |
| 452 |
| 32 Cl |
| ##STR159## |
| (CH2)3 OH |
| CH3 |
| orange 453 |
| 33 Cl |
| ##STR160## |
| (CH2)3 OC2 H5 |
| CH3 |
| orange 453 |
| 34 Cl |
| ##STR161## |
| ##STR162## |
| CH3 |
| orange 453 |
| 35 Cl (CH2)3 OH |
| (CH2)2 OH |
| CH3 |
| golden yellow |
| 452 |
| 36 Cl (CH2)3 OH |
| ##STR163## |
| CH3 |
| golden yellow |
| 455 |
| 37 Cl (CH2)3 OH |
| (CH2)2 OCH3 |
| CH3 |
| golden yellow |
| 453 |
| 38 Cl (CH 2)3 OH |
| (CH2)3 OCH3 |
| CH3 |
| golden yellow |
| 456 |
| 39 Cl (CH2)3 OH |
| (CH2)3 OC2 H5 |
| CH3 |
| golden yellow |
| 456 |
| 40 Cl (CH2)2 OH |
| (CH2)2 OH |
| CH3 |
| golden yellow |
| 452 |
| 41 Cl (CH2)2 OH |
| (CH2)3 OH |
| CH3 |
| golden yellow |
| 453 |
| 42 Cl (CH2)2 OH |
| ##STR164## |
| CH3 |
| golden yellow |
| 453 |
| 43 Cl (CH2)2 OH |
| (CH2)2 OCH3 |
| CH3 |
| golden yellow |
| 451 |
| 44 Cl (CH2)2 OH |
| (CH2)2 OCH3 |
| CH3 |
| golden yellow |
| 453 |
| 45 Cl (CH2)2 OH |
| (CH2)3 OC2 H5 |
| CH3 |
| golden yellow |
| 453 |
| 46 Cl (CH2)2 OH |
| C4 H9 (n) |
| CH3 |
| golden yellow |
| 456 |
| 47 Cl (CH2)2 OH |
| (CH2)3 OCH2 C6 H5 |
| CH3 |
| golden yellow |
| 455 |
| 48 Cl (CH2)2 OH |
| (CH2)2 C6 H 5 |
| Ch3 |
| golden yellow |
| 450 |
| 49 Cl (CH2)2 OH |
| ##STR165## |
| CH3 |
| golden yellow |
| 455 |
| 50 Cl (CH2)2 OH |
| ##STR166## |
| CH3 |
| golden yellow |
| 454 |
| 51 Cl C2 H5 |
| ##STR167## |
| CH3 |
| golden yellow |
| 451 |
| 52 Cl C2 H5 |
| C2 H5 |
| CH3 |
| golden yellow |
| 449 |
| 53 Cl (CH2)2 CN |
| (CH2)3 OH |
| CH3 |
| golden yellow |
| 450 |
| 54 Cl (CH2)5 CN |
| (CH2)3 OH |
| CH3 |
| golden yellow |
| 457 |
| 55 Cl (CH2)2 C6 H5 |
| (CH2)2 OH |
| CH3 |
| golden yellow |
| 448 |
| 56 Cl |
| ##STR168## |
| C4 H9 (n) |
| CH3 |
| golden yellow |
| 450 |
| 57 Cl CH2 CHCH 2 |
| (CH2)2 OH |
| CH3 |
| golden yellow |
| 452 |
| 58 Cl CH2 CHCH2 |
| (CH2)3 OH |
| CH3 |
| golden yellow |
| 454 |
| 59 Br (CH2)3 OH |
| (CH2)3 OH |
| CH3 |
| golden yellow |
| 457 |
| 60 CF3 |
| (CH2)3 OH |
| (CH2)3 OH |
| CH3 |
| golden yellow |
| 458 |
| 61 CF3 |
| (CH2)2 OCH3 |
| (CH2)2 OH |
| CH3 |
| golden yellow |
| 456 |
| 62 Cl |
| ##STR169## |
| (CH2)2 OH |
| CH3 |
| golden yellow |
| 453 |
| 63 Cl |
| ##STR170## |
| (CH2)3 OH |
| CH3 |
| golden yellow |
| 454 |
| 64 Cl |
| ##STR171## |
| (CH2)3 OH |
| CH3 |
| golden yellow |
| 455 |
| 65 Cl |
| ##STR172## |
| (CH2)2 OH |
| CH3 |
| golden yellow |
| 454 |
| 66 Cl (CH2)2 OCOCH3 |
| (CH2)2 OCOCH3 |
| CH3 |
| golden yellow |
| 450 |
| 67 Cl (CH2)3 OCHO |
| (CH2)3 OCHO |
| CH3 |
| golden yellow |
| 454 |
| 68 Cl (CH2)2 OCH3 |
| (CH2)3 OCHO |
| CH3 |
| golden yellow |
| 453 |
| 69 Cl (CH2)3 OCHO |
| (CH2)2 OCH3 |
| CH3 |
| golden yellow |
| 453 |
| 70 Cl (CH2)4 OH |
| (CH2)4 OH |
| CH3 |
| golden yellow |
| 457 |
| 71 Cl (CH2)4 OH |
| (CH2)3 OH |
| CH3 |
| golden yellow |
| 457 |
| 72 Cl (CH2)4 OH |
| (CH2)2 OH |
| CH3 |
| golden yellow |
| 456 |
| 73 Cl (CH2)4 OH |
| (CH2)2 OCH3 |
| CH3 |
| golden yellow |
| 456 |
| 74 Cl C3 H6 OC2 H4 OCH3 |
| ##STR173## |
| CH3 |
| orange 459 |
| 75 Cl C3 H6 OC2 H4 OCH3 |
| C6 H5 |
| CH3 |
| orange 458 |
| 76 Cl C3 H5 (OC2 H4)2 OCH3 |
| C6 H5 |
| CH3 |
| orange 458 |
| 77 Cl C3 H6 (OC2 H4)2 OCH3 |
| ##STR174## |
| CH3 |
| orange 460 |
| 78 Cl C2 H4 OC2 H4 OH |
| ##STR175## |
| CH3 |
| orange 458 |
| 79 Cl C2 H4 OC2 H4 OH |
| C6 H5 |
| CH3 |
| orange 457 |
| 80 Cl C6 H5 |
| C2 H4 OC2 H4 OH |
| CH3 |
| orange 456 |
| 81 Cl |
| ##STR176## |
| C2 H4 OC2 H4 OH |
| CH3 |
| orange 458 |
| 82 Cl |
| ##STR177## |
| C2 H4 OC2 H4 OH |
| CH3 |
| orange 458 |
| 83 Cl |
| ##STR178## |
| C2 H4 OC2 H4 OH |
| CH3 |
| orange 458 |
| __________________________________________________________________________ |
| TABLE 11 |
| __________________________________________________________________________ |
| ##STR179## |
| λmax |
| No. |
| R R1 R2 R3 Hue (nm) |
| __________________________________________________________________________ |
| 1 Cl C3 H6 OH |
| C6 H5 |
| C2 H4 OH |
| golden yellow |
| 435 |
| 2 Cl C3 H6 OH |
| C6 H5 |
| C2 H4 OCH3 |
| golden yellow |
| 433 |
| 3 Cl C3 H6 OH |
| C6 H5 |
| C3 H6 OCH3 |
| golden yellow |
| 436 |
| 4 Cl C3 H6 OH |
| C6 H5 |
| C2 H4 OC2 H5 |
| golden yellow |
| 434 |
| 5 Cl C3 H6 OH |
| C6 H5 |
| C2 H4 OC2 H4 OH |
| yellow 433 |
| 6 |
| Cl C3 H6 OH |
| C6 H5 |
| C2 H4 OC2 H4 OCH3 |
| yellow 433 |
| 7 Cl C3 H6 OH |
| C6 H5 |
| C3 H6 OC2 H4 OH |
| golden yellow |
| 435 |
| 8 Cl C3 H6 OH |
| C6 H5 |
| C3 H6 OC4 H8 OH |
| golden yellow |
| 436 |
| 9 Cl C2 H4 OH |
| C6 H5 |
| C2 H4 OCH3 |
| yellow 431 |
| 10 Cl C2 H4 OH |
| C6 H5 |
| C3 H6 OCH3 |
| yellow 432 |
| 11 Cl C2 H4 OH |
| C6 H5 |
| C3 H6 OC3 H7 |
| yellow 433 |
| 12 Cl C2 H4 OCH3 |
| C6 H5 |
| C2 H4 OCH3 |
| yellow 431 |
| 13 Cl C2 H4 OCH3 |
| C6 H5 |
| C3 H6 OCH3 |
| yellow 433 |
| 14 Cl C3 H6 OCH3 |
| C6 H5 |
| C3 H6 OCH3 |
| golden yellow |
| 434 |
| 15 Cl |
| ##STR180## C6 H5 |
| C3 H4 OCH3 |
| golden yellow |
| 435 |
| 16 Cl |
| ##STR181## C6 H5 |
| ##STR182## |
| golden yellow |
| 436 |
| 17 Br |
| ##STR183## C6 H5 |
| ##STR184## |
| golden yellow |
| 436 |
| 18 Br C3 H6 OH |
| C6 H6 |
| C3 H6 OH |
| golden yellow |
| 437 |
| 19 Cl C3 H6 OH |
| ##STR185## |
| C3 H6 OH |
| golden yellow |
| 436 |
| 20 Cl C3 H6 OH |
| ##STR186## |
| C3 H6 OH |
| golden yellow |
| 437 |
| 21 Cl C4 H8 OH |
| C6 H5 |
| C4 H8 OH |
| golden yellow |
| 438 |
| 22 Cl C2 H4 OH |
| ##STR187## |
| C2 H4 OH |
| golden yellow |
| 436 |
| 23 Cl |
| ##STR188## |
| ##STR189## |
| C2 H4 OH |
| yellow 434 |
| 24 CF3 |
| C3 H6 OH |
| C6 H5 |
| C3 H6 OH |
| golden yellow |
| 439 |
| 25 CF3 |
| C3 H6 OH |
| C6 H5 |
| C2 H4 OH |
| golden yellow |
| 439 |
| 26 CF3 |
| ##STR190## C6 H5 |
| C2 H4 OH |
| golden yellow |
| 439 |
| __________________________________________________________________________ |
| TABLE 12 |
| __________________________________________________________________________ |
| ##STR191## |
| No. |
| A R1 |
| R2 Hue λmax (nm) |
| __________________________________________________________________________ |
| 1 CH2 CH2 |
| Cl C2 H4 OH |
| golden yellow |
| 451 |
| 2 (CH2)3 |
| Cl C2 H4 OH |
| golden yellow |
| 453 |
| 3 (CH2)3 |
| Br C3 H6 OH |
| golden yellow |
| 455 |
| 4 (CH2)3 |
| Cl C2 H4 OC2 H4 OH |
| golden yellow |
| 455 |
| 5 (CH2)3 |
| Cl C2 H4 OCH3 |
| golden yellow |
| 455 |
| 6 (CH2)3 |
| Cl C3 H6 OCH3 |
| golden yellow |
| 456 |
| 7 (CH2)4 |
| Cl C2 H4 OH |
| golden yellow |
| 453 |
| 8 (CH2)4 |
| Cl C3 H6 OH |
| golden yellow |
| 456 |
| 9 (CH2)3 O(CH2)2 O(CH2)3 |
| Cl C2 H4 OH |
| golden yellow |
| 452 |
| 10 (CH2)3 O(CH2)2 O(CH2)3 |
| Cl C3 H6 OH |
| golden yellow |
| 453 |
| 11 (CH2)3 O(CH2)4 O(CH2)3 |
| Cl C3 H6 OH |
| golden yellow |
| 453 |
| 12 (CH2)3 O(CH2)4 O(CH2)3 |
| Cl C2 H4 OCH3 |
| golden yellow |
| 452 |
| 13 (CH2)3 O(CH2)4 O(CH2)3 |
| Br C3 H6 OCH3 |
| golden yellow |
| 454 |
| __________________________________________________________________________ |
| TABLE 13 |
| __________________________________________________________________________ |
| ##STR192## |
| λmax |
| No. |
| R1 |
| R2 |
| R3 |
| R4 R5 |
| Hue (nm) |
| __________________________________________________________________________ |
| 1 N(CH3)2 |
| H H CH2 CH2 OH |
| CH2 CH2 OH |
| orange |
| 2 N(CH3)2 |
| H Cl |
| CH2 CH2 OH |
| CH2 CH2 OH |
| orange |
| 430 |
| 3 N(CH3)2 |
| Cl |
| Cl |
| CH2 CH2 OH |
| CH2 CH2 OH |
| orange |
| 463 |
| 4 N(C2 H5)2 |
| Cl |
| Cl |
| CH2 CH2 OH |
| CH2 CH2 OH |
| orange |
| 463 |
| 5 N(C2 H5)2 |
| H Cl |
| CH2 CH2 OH |
| CH2 CH2 OH |
| orange |
| 461 |
| 6 N(C2 H5)2 |
| H Cl |
| C3 H6 OH |
| C3 H6 OH |
| orange |
| 432 |
| 7 N(CH3)2 |
| Cl |
| Cl |
| C2 H4 OCH3 |
| C3 H6 OH |
| orange |
| 463 |
| 8 N(CH3)2 |
| Cl |
| Cl |
| C2 H4 OCH3 |
| C2 H4 OCH3 |
| orange |
| 462 |
| 9 N(CH3)2 |
| Cl |
| Cl |
| C3 H6 OCH3 |
| C3 H6 OCH3 |
| orange |
| 465 |
| 10 N(CH3)2 |
| Cl |
| Cl |
| ##STR193## C3 H6 OCH3 |
| orange |
| 462 |
| 11 N(CH3)2 |
| Cl |
| Cl |
| ##STR194## C2 H4 OH |
| orange |
| 461 |
| 12 N(CH3)2 |
| Cl |
| Cl |
| ##STR195## C2 H5 |
| orange |
| 466 |
| 13 N(CH3)2 |
| Cl |
| Cl |
| ##STR196## |
| ##STR197## |
| orange |
| 467 |
| 14 N(C2 H5)2 |
| Cl |
| Cl |
| ##STR198## |
| ##STR199## |
| orange |
| 467 |
| 15 N(C2 H5)2 |
| H H |
| ##STR200## |
| ##STR201## |
| orange |
| 453 |
| 16 N(C2 H5)2 |
| H H |
| ##STR202## C6 H5 |
| orange |
| 452 |
| 17 N(C2 H5)2 |
| H H C2 H4 OC2 H4 OH |
| C6 H5 |
| orange |
| 452 |
| 18 N(CH3)2 |
| H H C2 H4 OC2 H4 OH |
| C6 H5 |
| orange |
| 452 |
| 19 CH3 |
| H Cl |
| ##STR203## C6 H5 |
| orange |
| 444 |
| 20 CH3 |
| H Cl |
| ##STR204## |
| ##STR205## |
| orange |
| 445 |
| 21 N(CH3)2 |
| Cl |
| Cl |
| C3 H6 OC2 H4 OCH3 |
| C3 H6 OCH3 |
| orange |
| 465 |
| 22 NHC4 H9 |
| Cl |
| Cl |
| ##STR206## C6 H5 |
| orange |
| 463 |
| __________________________________________________________________________ |
| TABLE 14 |
| ______________________________________ |
| ##STR207## |
| λmax |
| No. R1 R2 Hue (nm) |
| ______________________________________ |
| 1 Cl C2 H4 OC4 H9 |
| yellow |
| 426 |
| 2 Cl C3 H6 OC4 H9 |
| yellow |
| 427 |
| 3 Cl C4 H9 (n) |
| yellow |
| 428 |
| 4 Cl C3 H6 OC2 H5 |
| yellow |
| 426 |
| 5 Cl C3 H6 OCH3 |
| yellow |
| 427 |
| 6 Cl C3 H6 OC2 H4 OCH3 |
| yellow |
| 427 |
| 7 CH3 |
| C3 H6 OC2 H4 OCH3 |
| yellow |
| 427 |
| 8 CH3 |
| C3 H6 OCH3 |
| yellow |
| 427 |
| 9 CH3 |
| C3 H6 OC2 H5 |
| yellow |
| 427 |
| 10 CH3 |
| C3 H6 OC2 H4 OH |
| yellow |
| 427 |
| 11 Cl C3 H6 OC4 H8 OH |
| yellow |
| 427 |
| 12 CH3 |
| C3 H6 OC4 H8 OH |
| yellow |
| 427 |
| ______________________________________ |
| TABLE 15 |
| ______________________________________ |
| ##STR208## |
| λmax |
| No. R1 R2 R3 Hue (nm) |
| ______________________________________ |
| 1 C2 H4 OCH3 |
| CH3 CH3 yellow |
| 418 |
| 2 C2 H4 OCH3 |
| C2 H5 |
| C2 H5 |
| yellow |
| 419 |
| 3 C3 H6 OCH3 |
| C2 H5 |
| C2 H5 |
| yellow |
| 420 |
| 4 C3 H6 OCH3 |
| CH3 CH3 yellow |
| 418 |
| 5 C3 H6 OC2 H5 |
| CH3 CH3 yellow |
| 418 |
| 6 C3 H6 OC2 H5 |
| C2 H5 |
| C2 H5 |
| yellow |
| 420 |
| ##STR209## C2 H5 |
| C2 H5 |
| yellow |
| 419 |
| ##STR210## C2 H5 |
| C2 H5 |
| yellow |
| 420 |
| ##STR211## C4 H9 (n) |
| C4 H9 (n) |
| yellow |
| 422 |
| ______________________________________ |
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| Feb 15 1985 | BASF Aktiengesellschaft | (assignment on the face of the patent) | / |
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